Development of a molecularly imprinted photoelectrochemical sensing platform based on NH2-MIL-125(Ti)–TiO2 composite for the sensitive and selective determination of oxtetracycline

Abstract

In this work, a molecularly imprinted photoelectrochemical (MIP-PEC) sensor based on a novel PEC composite of metal-organic frameworks (MOFs) and TiO₂ (NH₂-MIL-125(Ti)–TiO₂) was established for the ultrasensitive and selective detection of oxytetracycline (OTC). This is the first attempt of applying MOFs in the construction of MIP-PEC sensor. The NH₂-MIL-125(Ti)–TiO₂ was synthesized by a simple one-step solvothermal method and modified onto the surface of indium tin oxide (ITO) electrode as the photosensitive layer. Subsequently, molecularly imprinted polymer (MIP) was modified as recognition element by electropolymerization. The NH₂-MIL-125(Ti)–TiO₂ showed an enhanced photocurrent response due to stronger light absorption capacity and matched energy band. Furthermore, MIP greatly improved the selectivity and sensitivity of the constructed PEC sensor. The photocurrent response of the MIP-PEC sensor was reduced after OTC recognition because the specific binding of OTC to the imprinted cavities blocked the electron transfer of the electrode. Under optimal experimental conditions, the MIP-PEC sensor exhibited a wide detection range from 0.1 nM to 10 μM with a low limit of detection (LOD) of 60 pM, as well as certain reproducibility, stability and good applicability in real samples. The proposed sensor provides ideas for the application of MOFs in the construction of PEC sensors and will offer an alternative method for the detection of other pollutants in the field of food safety.